Degradable Foam-Containing Tires, Related Methods And Kits For Adding Degradable Foam To Tires

ABSTRACT

Disclosed herein are kits for use in adding degradable foam to a tire, methods for preparing a degradable foam-containing tire, tires containing degradable foam, and methods for degrading the degradable foam in tires containing degradable foam. The degradable foam comprises a combination of (i) at least one di- or polyisocyanate, (ii) at least one polysiloxane diol, at least one polysiloxane diamine, or a combination thereof, and (iii) optionally at least one polyol.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a divisional of U.S. application Ser. No. 15/746,809filed on Jan. 23, 2021, and which has been assigned U.S. Pat. No.11,559,958, which is a U.S. national stage of International ApplicationNumber PCT/US2016/042762 filed on Jul. 18, 2016, which claims priorityto and any other benefit of U.S. Provisional Patent Application Ser. No.62/196102 filed Jul. 23, 2015, the entire disclosure of each of which isincorporated by reference herein.

FIELD

The present application is directed to kits for use in adding degradablefoam to a tire, methods for preparing a degradable foam-containing tire,tires containing degradable foam, and methods for degrading thedegradable foam in tires containing degradable foam.

BACKGROUND

The addition of polyurethane foam to pneumatic tires can provide certainadvantages such as improved tread wear and elimination of flat tiresfrom punctures. However, the presence of the polyurethane foam insidethe tire presents certain challenges when the foam-filled tire reachesthe end of its life and needs to be separated from the wheel.

SUMMARY

Disclosed herein are kits for use in adding degradable foam to a tire,methods for preparing a degradable foam-containing tire, tirescontaining degradable foam, and methods for degrading the degradablefoam in tires containing degradable foam.

In a first embodiment, a kit for use in adding degradable foam to a tireis provided. The kit comprises (a) a first component comprising at leastone di- or polyisocyanate, and (b) a second component comprising (i) atleast one polysiloxane diol, at least one polysiloxane diamine, or acombination thereof, and (ii) optionally at least one polyol.

In a second embodiment, a method for preparing a degradablefoam-containing tire is provided. The method comprises (a) providing atire comprising at least a wheel, a rubber carcass, and a valve stem;(b) combining ingredients comprising: (i) at least one di- orpolyisocyanate, (ii) at least one polysiloxane diol, at least onepolysiloxane diamine, or a combination thereof, and (iii) optionally atleast one polyol; and (c) adding the combined ingredients into therubber carcass through the valve stem, whereby the added combinedingredients form a degradable foam-containing tire comprising foam thatis capable of degradation upon contact with a source of fluoride anion.

In a third embodiment, a tire containing degradable foam is provided.The tire comprises a wheel, a rubber carcass comprising at least a treadportion and a sidewall portion, and optionally a valve stem; anddegradable foam comprised of a combination of: (i) at least one di- orpolyisocyanate, (ii) at least one polysiloxane diol, at least onepolysiloxane amine, or a combination thereof, and (iii) optionally atleast one polyol, the degradable foam contained in the interior of therubber carcass, wherein the degradable foam is capable of degradationupon contact with a source of fluoride anion.

In a fourth embodiment a method for degrading the degradable foam of atire containing degradable foam is provided. The tire comprises a wheel,a rubber carcass comprising at least a tread portion and a sidewallportion, and optionally a valve stem; and degradable foam comprised of acombination of: (i) at least one di- or polyisocyanate, (ii) at leastone polysiloxane diol, at least one polysiloxane amine, or a combinationthereof, and (iii) optionally at least one polyol, the degradable foamcontained in the interior of the rubber carcass. The method comprisescontacting the degradable foam with a solution comprising either: (a) asource of fluoride anion, or (b) an organic acid having a pKa of lessthan 2, an inorganic acid having a pKa of less than 2, or a combinationthereof and optionally a solvent for the acid.

DETAILED DESCRIPTION

Disclosed herein are kits for use in adding degradable foam to a tire,methods for preparing a degradable foam-containing tire, tirescontaining degradable foam, and methods for degrading the degradablefoam in tires containing degradable foam.

In a first embodiment, a kit for use in adding degradable foam to a tireis provided. The kit comprises (a) a first component comprising at leastone di- or polyisocyanate, and (b) a second component comprising (i) atleast one polysiloxane diol, at least one polysiloxane diamine, or acombination thereof, and (ii) optionally at least one polyol.

In a second embodiment, a method for preparing a degradablefoam-containing tire is provided. The method comprises (a) providing atire comprising at least a wheel, a rubber carcass, and a valve stem;(b) combining ingredients comprising: (i) at least one di- orpolyisocyanate, (ii) at least one polysiloxane diol, at least onepolysiloxane diamine, or a combination thereof, and (iii) optionally atleast one polyol; and (c) adding the combined ingredients into therubber carcass through the valve stem, whereby the added combinedingredients form a degradable foam-containing tire comprising foam thatis capable of degradation upon contact with a source of fluoride anion.

In a third embodiment, a tire containing degradable foam is provided.The tire comprises a wheel, a rubber carcass comprising at least a treadportion and a sidewall portion, and optionally a valve stem; anddegradable foam comprised of a combination of: (i) at least one di- orpolyisocyanate, (ii) at least one polysiloxane diol, at least onepolysiloxane amine, or a combination thereof, and (iii) optionally atleast one polyol, the degradable foam contained in the interior of therubber carcass, wherein the degradable foam is capable of degradationupon contact with a source of fluoride anion.

In a fourth embodiment a method for degrading the degradable foam of atire containing degradable foam is provided. The tire comprises a wheel,a rubber carcass comprising at least a tread portion and a sidewallportion, and optionally a valve stem; and degradable foam comprised of acombination of: (i) at least one di- or polyisocyanate, (ii) at leastone polysiloxane diol, at least one polysiloxane amine, or a combinationthereof, and (iii) optionally at least one polyol, the degradable foamcontained in the interior of the rubber carcass. The method comprisescontacting the degradable foam with a solution comprising either: (a) asource of fluoride anion, or (b) an organic acid having a pKa of lessthan 2, an inorganic acid having a pKa of less than 2, or a combinationthereof and optionally a solvent for the acid.

Definitions

The terminology as set forth herein is for description of theembodiments only and should not be construed as limiting the inventionas a whole.

As used herein, the terms “degrade,” “degraded,” and “degrading” (e.g.,degrading the foam or degraded foam) is intended to encompass entirelychanging the degradable foam inside the rubber carcass from a solid intoa pourable liquid as well as changing a portion of the degradable foaminside the rubber carcass from a solid into a pourable liquid. In otherwords, these terms should be understood to encompass changing asufficient portion of the foam inside the rubber carcass from a solidinto a pourable liquid to achieve separation of the wheel from therubber carcass and the foam. Degrading of the entire volume of foam froma solid into a pourable liquid is not necessarily required to achievethe separation. Moreover, a pourable liquid may include pieces or chunksof undegraded polyurethane foam. As non-limiting examples, ice waterwould be considered a pourable liquid whereas mayonnaise at 5° C. wouldnot be considered a pourable liquid.

As used herein, the term “majority” is used to describe an amount ofmore than 50% and the related term “at least a majority” is used todescribe an amount of more than 50% up to 100%. Additionally, the termsshould be understood to include all values within the range of greaterthan 50% to 100% (e.g., at least 55%, at least 60%, at least 65%, atleast 70%, at least 75%, at least 80%, at least 85%, at least 90%, atleast 95%, at least 98%, and at least 99%).

As used herein, the term “mounted” (i.e., mounted tire) is used todescribe a tire that is connected to a wheel, the connection may be, butis not necessarily, sufficient for use of the mounted tire on a vehicle.

Kits for Use in Adding Degradable Foam to a Tire

As discussed above, according to the first embodiment disclosed herein,a kit for use in adding degradable foam to a tire is provided. Incertain embodiments of the first embodiment, the tire for which the kitis intended to be used with is a pneumatic tire. According to the firstembodiment, the kit comprises a first component comprising at least onedi- or polyisocyanate, and a second component comprising at least onepolysiloxane diol, at least one polysiloxane diamine, or a combinationthereof; and optionally at least one polyol. As to the first component,by specifying that it comprises at least one di- or polyisocyanate itshould be understood to include embodiments wherein the first componentcomprises one diisocyanate, more than one diisocyanate, onepolyisocyanate, more than one polyisocyanate, one diisocyanate and onepolyisocyanate, more than one diisocyanate and one polyisocyanate, morethan one diisocyanate and more than one polyisocyanate, and onediisocyanate and more than one polyisocyanate. According to the firstembodiment, the first and second components are provided in separatecontainers; by separate is meant that the respective components are notin contact with each other. Moreover, the separate containers for thefirst and second components may have the same shape, same size, be madeof the same materials, be different shapes, be different sizes, be madeof different materials or combinations thereof. The separate containersmay take various forms that are not particularly limited as long as theyserve to contain their contents and maintain them separately until suchtime as their combination is required. For example, in certainembodiments of the first embodiment, the separate containers mayindependently be selected from at least one of the following: a bottle,a tube, a carton, a packet, a drum, or a can.

In certain embodiments of the first embodiment, the first component ofthe kit includes at least one additional ingredient, i.e., in additionto the at least one di- or polyisocyanate. In certain such embodiments,the first component of the kit further comprises at least one of thefollowing: at least one oil (e.g., hydrocarbon, mineral, or plant oil),one or more fillers (e.g., carbon black, silica, fiberglass), rubberparticles, one or more stabilizers (e.g., anti-oxidants, UVstabilizers), one or more plasticizers, one or more catalysts (asdiscussed below), or at least one foaming agent. In certain embodimentsof the first embodiment, the first component of the kit furthercomprises at least one oil.

In certain embodiments of the first embodiment, the kit furthercomprises at least one foaming agent. The at least one foaming agent maybe included as part of the first or second component or in a containerseparate from the containers of the first and second components.Suitable foaming agents for use in forming the degradable foam are wellknown to those of skill in the art, non-limiting examples and amounts ofwhich are discussed below. When the at least one foaming agent isprovided in a container separate from the containers of the first andsecond components, the particular container used is not especiallylimited and containers as discussed above for the first and secondcomponents may be utilized.

In certain embodiments of the first embodiment, the kit furthercomprises a third component comprising a source of fluoride anion usefulfor degrading a foam formed from the first and second components.Various sources of fluoride anion may be utilized, as discussed below.The particular container used for the third component is not especiallylimited and containers as discussed above for the first and secondcomponents may be utilized.

In certain embodiments, the kit may comprise at least four components,i.e., the first component, the second component, a third component(comprising a source of fluoride anion), and another component(comprising at least one of the additional ingredients discussed above).

Methods for Preparing Degradable Foam-Containing Tires

As discussed above, the second embodiment disclosed herein is directedto a method for preparing a degradable foam-containing tire. The methodcomprises (a) providing a tire comprising at least a wheel, a rubbercarcass, and a valve stem; (b) combining ingredients comprising: (i) atleast one di- or polyisocyanate, (ii) at least one polysiloxane diol, atleast one polysiloxane diamine, or a combination thereof, and (iii)optionally at least one polyol; and (c) adding the combined ingredientsinto the rubber carcass through the valve stem, whereby the addedcombined ingredients form a degradable foam-containing tire comprisingfoam that is capable of degradation upon contact with a source offluoride anion. In certain embodiments of the second embodiment, theingredients combined in (b) further comprise at least one additionalingredient, i.e., in addition to the at least one di- or polyisocyanate.In certain such embodiments, the at least one additional ingredientcomprises at least one of the following: at least one oil (e.g.,hydrocarbon, mineral, or plant oil), one or more fillers (e.g., carbonblack, silica, fiberglass), rubber particles, one or more stabilizers(e.g., anti-oxidants, UV stabilizers), one or more plasticizers, one ormore catalysts (as discussed below), or at least one foaming agent. Incertain embodiments of the second embodiment, the ingredients combinedin (b) further comprise at least one oil. In certain embodiments of thesecond embodiment, ingredients (i), (ii) and optionally (iii) arecombined within the tire, i.e., they are not pre-mixed prior to beingadded through the valve stem of the tire.

In certain embodiments of the second embodiment, the ingredientscombined in (b) further comprise at least one foaming agent. Suitablefoaming agents for use in forming the degradable foam are well known tothose of skill in the art, non-limiting examples and amounts of whichare discussed below.

The methods of the second embodiment may be, but are not necessarily,utilized with the kits of the first embodiment disclosed herein.

Tires Containing Degradable Foam

As discussed above, the third embodiment disclosed herein is directed toa tire containing degradable foam. The tire comprises a wheel, a rubbercarcass comprising at least a tread portion and a sidewall portion, andoptionally a valve stem; and degradable foam comprised of a combinationof: (i) at least one di- or polyisocyanate, (ii) at least onepolysiloxane diol, at least one polysiloxane amine, or a combinationthereof, and (iii) optionally at least one polyol, the degradable foamcontained in the interior of the rubber carcass, wherein the degradablefoam is capable of degradation upon contact with a source of fluorideanion. In certain embodiments, the tire is a pneumatic tire that has hadat least a majority of its air replaced with degradable foam.

The tires of the third embodiment may be prepared using the methods ofthe second embodiment or by methods that differ from the methods of thesecond embodiment. The methods of the second embodiment may be utilizedto produce tires according to the third embodiment or alternatively maybe utilized to produce tires that differ in certain aspects from thetires according to the third embodiment.

Methods for Degrading Degradable Foam of Degradable Foam-ContainingTires

As discussed above, the fourth embodiment disclosed herein is directedto methods for degrading the degradable foam of degradablefoam-containing tires. The degradable foam-containing tire comprises awheel, a rubber carcass comprising at least a tread portion and asidewall portion, and optionally a valve stem; and degradable foamcomprised of a combination of: (i) at least one di- or polyisocyanate,(ii) at least one polysiloxane diol, at least one polysiloxane amine, ora combination thereof, and (iii) optionally at least one polyol, thedegradable foam contained in the interior of the rubber carcass. Themethod comprises contacting the degradable foam with a solutioncomprising either: (a) a source of fluoride anion, or (b) an organicacid having a pKa of less than 2, an inorganic acid having a pKa of lessthan 2, or a combination thereof and optionally a solvent for the acid.The solution is also described herein as a degradant.

The amount of solution applied to the degradable foam inside the rubbercarcass may vary depending upon various factors such as the particulartype of solution utilized, the particular composition of the degradablefoam, the overall volume of degradable foam inside the tire carcass, thedimensions of the tire (e.g., overall tire diameter, sidewall height,tread width), and the time available for the degradation of the foam tooccur. Generally, larger volumes of foam will require larger volumes ofsolution and relatively larger tires (particularly those having highersidewall height or wider tread width) may require relatively largerratios of solution to foam to achieve the same approximate time fordegradation.

In certain embodiments of the first-third embodiments disclosed herein,the solution is applied to the degradable foam inside the rubber carcassin an amount sufficient to provide fluoride anion in an amount of about1% to about 100% (on a volume of source of fluoride anion to volume ofdegradable foam basis) or 1% to 100%. In certain embodiments of thefourth embodiment, the solution is applied to the degradable foam insidethe rubber carcass in an amount sufficient to provide fluoride anion inan amount of about 5% to about 100% (on a volume of source of fluorideanion to volume of degradable foam basis), including 5% to 100%, about5% to about 90%, 5% to 90%, about 5% to about 80%, 5% to 80%, about 5%to about 70%, 5% to 70%, about 5% to about 60%, 5% to 60%, about 5% toabout 50%, 5% to 50%, about 5% to about 40%, 5% to 40%, about 5% toabout 30%, 5% to 30%, about 5% to about 20%, 5% to 20%, about 5% toabout 15%, 5% to 15%, about 1% to about 20%, 1% to 20%, about 1% toabout 15%, 1% to 15%, about 1% to about 10%, and 1% to 10%. For purposesof determining the volume of foam inside the rubber carcass, it isintended that the dimensions of the tire can be utilized (e.g., bycalculating the volume of a torus having the dimensions of the tire) andthe assumption made that the volume inside the rubber carcass is atleast 95% filled with foam. The volume ratios provided herein areintended for application by using the density of the solution or thesolution ingredients at 25° C. Generally, the greater the relativeamount of polysiloxane as compared to polyol present in the foam, thegreater the relative amount of fluoride anion that may be used toachieve degradation in the same amount of time.

In certain embodiments of the first-third embodiments disclosed herein,the solution comprising the organic acid having a pKa of less than 2,inorganic acid having a pKa of less than 2, or a combination thereof andoptionally a solvent for the acid is applied to the degradable foaminside the rubber carcass in an amount sufficient to provide completesolubility of the acid in an amount of about 1% to about 50% (on avolume of solvent to volume of degradable foam basis) or 1-50%. Incertain embodiments of the fourth embodiment, the solution is applied tothe degradable foam inside the rubber carcass in an amount sufficient toprovide complete solubility of the acid in an amount of about 10% toabout 25% (on a volume of solvent to volume of degradable foam basis) or10-25%.

According to the methods of the fourth embodiment, the step ofcontacting the degradable foam with the specified solution may takevarious forms as long as the solution makes contact with the degradablefoam. In certain embodiments of the fourth embodiment, the solution isinjected into the degradable foam. In certain embodiments of the fourthembodiment, the solution is added through the valve stem, through thesidewall of the tire, through the tread of the tire, or by a combinationthereof In those embodiments where the solution is added through thesidewall of the tire, it may be added at one or more sidewall locationsand each location may be cut, punctured, pierced or some combinationthereof to facilitate the addition of the solution. As non-limitingexamples, the solution may be injected through the sidewall using aneedle, nozzle or other injection device, either through the intactsidewall or through a cut, puncture or other opening added for thepurpose of facilitating the addition of the solution to the degradablefoam. In those embodiments where the solution is added through the treadof the tire, it may be added at one or more tread locations and eachlocation may be cut, punctured, pierced or some combination thereof tofacilitate the addition of the solution. As non-limiting examples, thesolution may be injected through the tread using a needle, nozzle orother injection device, either through the intact tread or through acut, puncture or other opening added for the purpose of facilitating theaddition of the solution to the degradable foam. In certain embodimentsof the fourth embodiment disclosed herein, the foam inside the rubbercarcass is at least partially exposed to the outer environment prior toapplying the solution. Various methods of partially exposing thepolyurethane foam can be utilized, including cutting, puncturing, orpiercing the sidewall or tread of the tire. In certain embodiments ofthe first-third embodiments, the tire is placed on one side and a cut ismade (circumferentially) around a portion (preferably at least amajority) of the upper side of the tire exposing the foam inside; insuch embodiments, the lower side of the tire can act as a type ofcontainer to collect the degraded foam, thereby containing it oreliminating the need for use of another container to collect thedegraded foam. The foregoing description of methods for contacting thedegradable foam with the degradant or solution should be understood tobe applicable to certain embodiments of the first-third embodimentsdisclosed herein, in addition to the fourth embodiment.

In certain embodiments of the methods of the fourth embodiment, themethod comprises contacting the degradable foam with a solutioncomprising a source of fluoride anion. Various sources of fluoride anionexist and may be utilized in the solution according to the methods ofthe fourth embodiment. In certain embodiments of the fourth embodiment,the solution comprising a source of fluoride anion comprises hydrogenfluoride, at least one tetraalkylammonium fluoride, cesiumfluoride/caesium fluoride, a pyridine salt of hydrogen fluoride, or acombination thereof. Various tetraalkylammonium fluoride compounds aresuitable for use as the degradant in certain embodiments of the fourthembodiment and in certain embodiments applicable to the first-thirdembodiments disclosed herein (e.g., for the third component in kits ofthe first embodiment). In certain such embodiments, thetetraalkylammonium fluoride has the general formula:(C_(n)H_(2n+1))₄N⁺F⁻ where n is from 1 to 30, preferably n is from 1 to18 and more preferably n is from 1 to 12 particular examples of whichinclude, but are not limited to, tetramethylammonium fluoride,tetraethylammonium fluoride, tetrabutylammonium fluoride,tetrapentylammonium fluoride, tetrahexylammonium fluoride,tetraheptylammonium fluoride, tetraoctylammonium fluoride,tetranonylammonium fluoride, tetradecylammonium fluoride,tetraisopropylammonium fluoride, tetraisobutylammonium fluoride,tetra(tert-butyl)ammonium fluoride, tetra(tert-pentyl)ammonium fluoride,and combinations thereof. The preceding discussion of sources offluoride anion should be understood to be applicable to thoseembodiments of the first-third embodiments that involve the use of such.

In certain embodiments of the methods of the fourth embodiment, themethod comprises contacting the degradable foam with a solutioncomprising an organic acid having a pKa of less than 2, an inorganicacid having a pKa of less than 2, or a combination thereof, andoptionally a solvent for the acid. The pKa values referred to herein areof the acid in water. As used herein the term “organic acid” refers toacids containing carbon and hydrogen and having at least one COOH moietyand the term “inorganic acid” refers to acids lacking carbon.Non-limiting examples of suitable organic and inorganic acids having apKa of less than 2 for use in the solution include sulfonic acids (e.g.,camphorsulfonic acid, p-toluene sulfonic acid, trifluoromethane sulfonicacid, methane sulfonic acid), hydrochloric acid, and hydrobromic acid.As used herein the term “sulfonic acid” refers to an acid having theformula RS(═O)₂OH wherein R is selected from alkyl and aryl (eitheroptionally substituted with one or more halogen). Optionally, thesolution comprises at least one solvent capable of dissolving the acid(such as a protic or aprotic solvent).

The methods of the fourth embodiment disclosed herein may be, but arenot necessarily, utilized on the tires of the third embodiment disclosedherein.

Di- and Polyisocyanates

As discussed above, according to the embodiments of the first-fourthembodiments disclosed herein, the kits disclosed herein comprise, thedegradable foam comprises or is prepared by combining ingredientscomprising at least one di- or polyisocyanate. As used herein, the termdiisocyanate is used to describe compounds that contain two isocyanatemoieties (i.e., two —C(═O)N(H)— moieties) and the term polyisocyanate isused to describe compounds that contain more than two isocyanatemoieties. Various compounds suitable for use as the at least one di- orpolyisocyanate are well known. In certain embodiments of thefirst-fourth embodiments disclosed herein, the at least one di- orpolyisocyanate is selected from aliphatic di- or polyisocyanates,aromatic di- or polyisocyanates, araliphatic di- or polyisocyanates,cycloaliphatic, di- or polyisocyanates, and combinations thereof.Suitable compounds for each of the foregoing types of di- andpolyisocyanates are well known. Non-limiting examples of suitablearomatic diisocyanates include toluene diisocyanate (also known astolylene diisocyanate or TDI), diphenylmethane diisocyanate (also knownas methylenebis(phenyl isocyanate) or MDI), 1,3′-dimethyl-4,4-biphenyldiisocyanate (also known as TODI), 1,4-para-phenylene diisocyanate (alsoknown as PPDI), and 1,5-naphthalene diisocyanate; in certain embodimentsof the first-fourth embodiments the at least one di- or polyisocyanatecomprises at least one of the foregoing. Commercially available sourcesof toluene diisocyanate may include one or more of: 2,4-toluenediisocyanate, 2,6-toluene diisocyanate, and combinations thereof.Commercially available sources of MDI may include one or more of 2,2′-,2,4′-, and 4,4′-diphenylmethane diisocyanate. Non-limiting examples ofsuitable aliphatic diisocyanates include butane diisocyanate, pentanediisocyanate, hexane diosocyanate, 4-isocyanatomethyl-1,8-octanediisocyanate (also known as triisocyanatononane or TIN), 1,4-butylenediisocyanate, 1,12-dodecamethylene diisocyanate, 1,10-decamethylenediisocyanate, 2-butyl-2-ethylpentamethylene diisocyanate,2,4,4-trimethylhexamethylene diisocyanate, 2,2,4-trimethylhexamethylenediisocyanate, and hexamethylene diisocyanate (also known as hexanediisocyanate or HDI); in certain embodiments of the first-fourthembodiments the at least one di- or polyisocyanate comprises at leastone of the foregoing. Non-limiting examples of suitable cycloaliphaticdiisocyanates include isophorone diisocyanate (IPDI),2-isocyanatopropylcyclohexyl isocyanate, 2,4′-methylenebis(cyclohexyl)diisocyanate, 4-methylcyclohexane,4,4′-methylene-bis(cyclohexylisocyanate (also known as hydrogenated MDIor H12 MDI), 3,5,5-trimethyl-1-isocyanato-3-isocyanatomethylcyclohexane(also known as isophorone diisocyanate or IPDI), 1,3- and1,4-bis(isocyanatomethyl)cyclohexane (also known as (H₆XDI),1,3-diisocyanate (H-TDI); in certain embodiments of the first-fourthembodiments the at least one di- or polyisocyanate comprises at leastone of the foregoing. Non- limiting examples of suitable araliphatic di-or polyisocyanates include tetramethylxylylene diisocyanate (also knownas TMDXI), m-xylylene diisocyanate, 3,3′-dimethoxy-4,4′-biphenylenediisocyanate, polymeric diphenylmethane diisocyanate,2,4-diisocyanatodiphenyl sulfide, diethyldiisocyanatobenzene; in certainembodiments of the first-fourth embodiments the at least one di- orpolyisocyanate comprises at least one of the foregoing. In certainembodiments of the first-fourth embodiments, the at least one di- orpolyisocyanate may comprise a combination of one or more of theforegoing.

Polysiloxane Diols, Polysiloxane Diamines, and Combinations Thereof

As discussed above, according to the embodiments of the first-fourthembodiments disclosed herein, the kits disclosed herein comprise, thedegradable foam comprises or is prepared by combining ingredientscomprising at least one polysiloxane diol, at least one polysiloxanediamine, or a combination thereof. The use of the phrase at least onepolysiloxane diol, at least one polysiloxane diamine, or a combinationthereof is meant to encompass embodiments where one polysiloxane diol isused, more than one polysiloxane diol is used, one polysiloxane diamineis used, more than one polysiloxane diamine is used, one polysiloxanediol and one polysiloxane diamine are used, more than one polysiloxanediol and one polysiloxane diamine are used, one polysiloxane diol andmore than one polysiloxane diamine are used, and more than onepolysiloxane diol and more than one polysiloxane diamine are used. Asused herein, the term polysiloxane is used to describe compounds thatcontain at least three Si each bonded to at least two oxygen.

In certain embodiments of the first-fourth embodiments disclosed herein,the at least one polysiloxane diol, at least one polysiloxane diamine,or a combination thereof comprises at least one polysiloxane diol havingthe formula

HO—(R⁵)_(m)—Si(R¹)(R³)—[O—Si(R²)(R⁴)]_(n)—(R⁶)_(o)—OH

wherein R¹, R², R³, R⁴, R⁵ and R⁶ are the same or different and areindependently selected from optionally substituted with one or moreheteroatoms straight chain, branched or cyclic, saturated or unsaturatedhydrocarbon radicals, n is an integer of 2 to 365, m is an integer of 0or 1, and o is an integer of 0 or 1. In certain embodiments, m and o areboth 1 and R⁵ and R⁶ are independently selected from optionallysubstituted straight chain, branched or cyclic, saturated or unsaturatedhydrocarbon radicals having 1 to 12 carbons. In certain embodiments,none of R¹, R², R³, R⁴, R⁵, and R⁶ contain any heteroatom. In certainembodiments, each of R¹, R², R³, R⁴ is independently selected from alkylhydrocarbons. Examples of straight chain and branched saturatedhydrocarbon suitable for use as R¹, R², R³, R⁴ or a combination thereofinclude alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl,isobutyl, sec-butyl, tert-butyl, amyl, isoamyl, secamyl,1,2-dimethylpropyl, 1,1-dimethylpropyl, pentyl, hexyl, 4-methylpentyl,1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 1,1-dimethylbutyl,2,2-dimethylbutyl, 3,3-dimethylbutyl, 1,2-dimethylbutyl,1,3-dimethylbutyl, 1,2,2-trimethylpropyl, 1,1,2-trimethylpropyl, heptyl,5-methylhexyl, 1-methylhexyl, 2,2-dimethylpentyl, 3,3-dimethylpentyl,4,4-dimethylpentyl, 1,2-dimethylpentyl, 1,3-dimethylpentyl,1,4-dimethylpentyl, 1,2,3-trimethylbutyl, 1,1,2-trimethylbutyl,1,1,3-trimethylbutyl, octyl, 6-methylheptyl, 1-methylheptyl,1,1,3,3-tetramethylbutyl, nonyl, 1-, 2-, 3-, 4-, 5-, 6- or7-methyloctyl, 1-, 2-, 3-, 4- or 5-ethylheptyl, 1-, 2- or3-prophylhexyl, decyl, 1-, 2-, 3-, 4-, 5-, 6-, 7- and 8-methylnonyl, 1-,2-, 3-, 4-, 5- or 6-ethyloctyl, 1-, 2-, 3- or 4-propylheptyl, undecyl1-, 2-, 3-, 4-, 5-, 6,7-, 8- or 9-methyldecyl, 1-, 2-, 3-, 4-, 5-, 6- or7-ethylnonyl, 1-, 2-, 3-, 4- or 5-propyloctyl, 1-, 2- or 3-butylheptyl,1-pentylhexyl, dodecyl, 1-, 2-, 3-, 4-, 5-, 6-, 7-, 8-, 9- or10-methylundecyl, 1-, 2-, 3-, 4-, 5-, 6-, 7- or 8-ethyldecyl, 1-, 2-,3-, 4-, 5- or 6-propylnonyl, 1-, 2-, 3- or 4-butyloctyl,1,2-pentylheptyl and the like. Examples of cyclic saturated hydrocarbonssuitable for use as R¹, R², R³, R⁴, or a combination thereof includecyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl,cyclooctyl, cyclononyl and cyclodecyl and the like.

In certain embodiments of the first-fourth embodiments disclosed herein,the at least one polysiloxane diol, at least one polysiloxane diamine,or a combination thereof comprises at least one polysiloxane diaminehaving the formula

H₂N—(R⁵)_(m)—Si(R¹)(R³)—[O—Si(R²)(R⁴)]_(n)—(R⁶)_(o)—NH₂

wherein R¹, R², R³, R⁴, R⁵, and R⁶ are the same or different and areindependently selected from optionally substituted with one or moreheteroatoms straight chain, branched or cyclic, saturated or unsaturatedhydrocarbon radicals, n is an integer of 2 to 365, m is an integer of 0or 1, and o is an integer of 0 or 1. In certain embodiments, m and o areboth 1 and R⁵ and R⁶ are independently selected from optionallysubstituted straight chain, branched or cyclic, saturated or unsaturatedhydrocarbon radicals having 1 to 12 carbons. In certain embodiments,none of R¹, R², R³, R⁴, R⁵, and R⁶ contain any heteroatom. In certainembodiments, each of R¹, R², R³, R⁴ is independently selected from alkylhydrocarbons. Examples of suitable R¹, R², R³, R⁴ include thosediscussed above in the section on polysiloxane diols. Variouspolysiloxane diamines are commercially available from suppliers such asSigma Aldrich Corporation (St. Louis, Miss.). Non-limiting examples ofpolysiloxane diamines suitable for use in certain embodiments of thefirst-fourth embodiments disclosed herein include poly(dimethylsiloxane)diamine, poly(methylphenyl siloxane) diamine, poly(epoxy-modifiedsiloxane) diamine, poly(dimethyl siloxane)co-poly(diphenyl siloxane)diamine, polysiloxane-polyether diamine copolymer,poly(dimethylsiloxane) bis(3-aminopropyl) terminated, and combinationsthereof.

Polyols

As discussed above, according to certain embodiments of the first-fourthembodiments disclosed herein, the kits disclosed herein comprise, thedegradable foam comprises or is prepared by combining ingredientscomprising at least one polyol along with the at least one di- orpolyisocyanate, and at least one polysiloxane diol, at least onepolysiloxane diamine, or a combination thereof. In other words, the atleast one polyol is an optional ingredient in the degradable foam. Asused herein, a polyol describes a compound that is reactive with theNC(═O) functionality of the di- or polyisocyanate and that has a mean OHor NH functionality of at least 2. In those embodiments of thefirst-fourth embodiments disclosed herein when at least one polyol isutilized, the degradable foam that results from the mixture ofingredients can be considered to be a degradable polyurethane foam. Incertain embodiments of the first-fourth embodiments when the at leastone polyol is utilized it is selected from alkylene polyols, arylenepolyols, polyether polyols, polyester polyols, polycarbonate polyols,polybutadiene polyols, polyamines, polyether polyamines, hydrocarbonpolyols, and combinations thereof. Non-limiting examples of alkylenepolyols and arylene polyols include diols (e.g., 1,2-ethanediol,1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,6-hexanediol,1,8-octanediol, 1,9-nonadiol, 1,10-decandiol, 1,12-dodecanediol,1,4-cyclohexane dimethanol, p-xyleneglycol, 1,4-bis (2-hydroxyethoxy)benzene), triols (e.g., glycerol, trimethylolpropane), and tetraols(e.g., pentaerythritol). Non-limiting examples of polyether polyolsinclude those with the formula HO—[(CH₂)_(m)—O]_(n)—H wherein m is aninteger of 28 or more, preferably 4 to 18 and n is an integer of 2 to 50including poly(tetramethylene oxide), polyhexamethylene oxide (alsoknown as PHMO), polyheptamethylene diol, polyoctamethylene oxide (POMO),polydecamethylene oxide (PDMO), and combinations thereof. Non-limitingexamples of polycarbonate polyols include poly(alkylenecarbonates) suchas poly(hexamethylene carbonate) and poly(decamethylene carbonate);polycarbonates prepared by reacting alkylene carbonate with alkanediolsfor example 1,4-butanediol, 1,10-decandiol, 1,6-hexanediol and/or2,2-diethyl 1,3-propanediol; and silicon based polycarbonates preparedby reacting alkylene carbonate with 1,3-bis(4-hydroxybutyl)-1,1,3,3-tetramethyldisiloxane (BHTD) and/oralkanediols.

Various polyols suitable for use in certain embodiments of thefirst-fourth embodiments disclosed herein are commercially availablefrom supplier such as Sigma Aldrich Corporation (St. Louis, Miss.).Moreover, various methods for producing polyols suitable for use incertain embodiments of the first-fourth embodiments disclosed herein arewell known. For example, polyether polyols are obtainable byalkoxylation of suitable starter molecules with base catalysis or usingdouble metal cyanide compounds (DMC compounds). Suitable startermolecules for the preparation of polyether polyols are, for example,simple, low molecular weight polyols, water, organic polyamines havingat least two N—H bonds or arbitrary mixtures of such starter molecules.Preferred starter molecules for the preparation of polyether polyols byalkoxylation, in particular by the DMC process, are in particular simplepolyols such as ethylene glycol, 1,3-propylene glycol and1,4-butanediol, 1,6-hexanediol, neopentyl glycol,2-ethyl-1,3-hexanediol, glycerol, trimethylolpropane, pentaerythritol aswell as low molecular weight, hydroxyl-group containing esters of suchpolyols with dicarboxylic acids of the type mentioned by way of examplebelow or low molecular weight ethoxylation or propoxylation products ofsuch simple polyols or arbitrary mixtures of such modified or unmodifiedalcohols. Alkylene oxides suitable for the alkoxylation are inparticular ethylene oxide and/or propylene oxide, which can be used inthe alkoxylation in any desired sequence or also in admixture. Polyesterpolyols can be prepared by polycondensation of low molecular weightpolycarboxylic acid derivatives, such as, for example, succinic acid,adipic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioicacid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride,tetrachlorophthalic anhydride, endomethylenetetrahydrophthalicanhydride, glutaric anhydride, maleic acid, maleic anhydride, fumaricacid, dimer fatty acid, trimer fatty acid, phthalic acid, phthalicanhydride, isophthalic acid, terephthalic acid, citric acid ortrimellitic acid, with low molecular weight polyols, such as, forexample, ethylene glycol, diethylene glycol, neopentyl glycol,hexanediol, butanediol, propylene glycol, glycerol, trimethylolpropane,1,4-hydroxymethylcyclohexane, 2-methyl-1,3-propanediol,1,2,4-butanetriol, triethylene glycol, tetraethylene glycol,polyethylene glycol, dipropylene glycol, polypropylene glycol,dibutylene glycol and polybutylene glycol, or by ring -openingpolymerization of cyclic carboxylic acid esters, such as E-caprolactone.In addition, hydroxycarboxylic acid derivatives, such as, for example,lactic acid, cinnamic acid or w-hydroxycaproic acid, can also bepolycondensed to polyester polyols. However, polyester polyols ofoleochemical origin can also be used. Such polyester polyols can beprepared, for example, by complete ring opening of epoxidizedtriglycerides of an at least partially olefinically unsaturatedfatty-acid-containing fatty mixture with one or more alcohols havingfrom 1 to 12 carbon atoms and by subsequent partial transesterificationof the triglyceride derivatives to alkylester polyols having from 1 to12 carbon atoms in the alkyl radical. Polyacrylate polyols can beprepared by radical polymerization of hydroxyl-group-containing,olefinically unsaturated monomers or by radical copolymerization ofhydroxyl-group-containing, olefinically unsaturated monomers withoptionally other olefinically unsaturated monomers, such as, forexample, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate,isobornyl acrylate, methyl methacrylate, ethyl methacrylate, butylmethacrylate, cyclohexyl methacrylate, isobornyl methacrylate, styrene,acrylic acid, acrylonitrile and/or methacrylonitrile. Suitablehydroxyl-group-containing, olefinically unsaturated monomers include2-hydroxyethylacrylate, 2-hydroxyethyl methacrylate, the hydroxypropylacrylate isomer mixture obtainable by addition of propylene oxide toacrylic acid, and the hydroxypropylmethacrylate isomer mixtureobtainable by addition of propylene oxide to methacrylic acid. Suitableradical initiators are those from the group of the azo compounds, suchas, for example, azoisobutyronitrile (AIBN), or from the group of theperoxides, such as, for example, di-tert-butyl peroxide.

Amounts of Di- or Polyisocyanate(s); Polysiloxane(s); and Polyol(s)

As discussed above, according to the first-fourth embodiments disclosedherein, the kits disclosed herein comprise, the degradable foamcomprises or is prepared by combining ingredients comprising (i) atleast one di- or polyisocyanate; (ii) at least one polysiloxane diol, atleast one polysiloxane diamine, or a combination thereof; and (iii)optionally at least one polyol. Varying amounts of each component can beutilized.

In those embodiments where the at least one polyol is present, it can beutilized in varying amounts. In certain embodiments of the first-fourthembodiments disclosed herein, the polyol is present and it comprisesabout 1 to about 95% by volume of the total combined volume of the atleast one polyol and at least one polysiloxane diol, at least onepolysiloxane diamine, or a combination thereof In certain embodiments ofthe first-fourth embodiments disclosed herein, the at least one polyolis present and it comprises about 1 to about 95% by weight of the totalcombined amount (by weight) of the at least one polyol and at least onepolysiloxane diol, at least one polysiloxane diamine, or a combinationthereof In certain embodiments of the first-fourth embodiments disclosedherein, the at least one polyol is present and it comprises about 1 toabout 95%, 1 to 95%, about 1 to about 75%, 1 to 75%, about 1 to about50%, 1 to 50%, about 5 to about 95%, 5 to 95%, about 5 to about 75%, 5to 75%, about 5 to about 50%, 5 to 50%, about 10 to about 95%, 10 to95%, about 10 to about 75%, 10 to 75%, about 10 about 50%, 10 to 50%,about 10 to about 40%, 10 to 40%, about 10 to about 25%, 10 to 25%,about 15 to about 95%, 15 to 95%, about 15 to about 75%, 15 to 75%,about 15 to about 50%, 15 to 50%, about 15 to about 40%, 15 to 40%,about 15 to about 25%, or 15 to 25%, each amount by weight of the totalcombined amount (by weight) of the at least one polyol and at least onepolysiloxane diol, at least one polysiloxane diamine, or a combinationthereof. As a non-limiting example, an amount of about 15 to about 25%by weight of the at least one polyol would be met by the use of 85 partsby weight of the at least one polysiloxane diol, at least onepolysiloxane diamine, or a combination thereof with 15 parts by weightof the at least one polyol, and also by the use of 75 parts by weight ofthe at least one polysiloxane diol, at least one polysiloxane diamine,or a combination thereof with 25 parts by weight of the at least onepolyol, respectively. In certain embodiments of the first-fourthembodiments disclosed herein, the at least one polyol is present andcomprises a majority by weight of the total combined amount (by weight)of the at least one polyol and at least one polysiloxane diol, at leastone polysiloxane diamine, or a combination thereof. In certainembodiments of the first embodiment, the second component of the kitcomprises about 1 to about 50%, 1 to 50%, about 15 to about 25%, or 15%to 25% by weight of the at least one polyol, based upon the combinedtotal weight of at least one polyol and at least one polysiloxane diol,at least one polysiloxane diamine, or a combination thereof.

For purposes of the following discussion, the first component should beunderstood as including the at least one di- or polyisocyanate and thesecond component should be understood as including the at least onepolysiloxane diol, at least one polysiloxane diamine, or a combinationthereof as well as any polyol that is utilized. According to thefirst-fourth embodiments, the relative amount of the first component andsecond component contained in the degradable foam, in the kit, or usedto prepare the degradable foam can vary widely. In certain embodimentsof the first-fourth embodiments disclosed herein, the ratio of the firstcomponent to the second component is from greater than 1:1 up to about4:1, including up to 4:1, about 1.2:1 to about 4:1, 1.2:1 to 4:1, about1.5:1 to about 4:1, 1.5:1 to 4:1, about 2:1 to about 4:1, 2:1 to 4:1,about 1.5:1 to about 3:1, 1.5:1 to 3:1, about 2:1 to about 3:1, and 2:1to 3:1. As those of skill in the art will understand, the ratio of thefirst component to second component can be varied depending upon theultimate use for the foam-filled tire with relatively higher amounts ofthe first component (di- or polyisocyanate) producing a foam that isrelatively less compressible.

Foaming Agent

In certain embodiments of the first-fourth embodiments, a foaming agentwill be included in the ingredients of the kit, ingredients of the foamor ingredients used to prepare the foam. In certain embodiments of thefirst-fourth embodiments, the foaming agent comprises water which ispresent in a sufficient amount in one or more of the other ingredients(e.g., at least one polyol) that no separate foaming agent need beadded. In other embodiments of the first-fourth embodiments, a separatefoaming agent is utilized and it can be combined with the at least onedi- or polyisocyanate (e.g., present in the first component of the firstembodiment), with the at least one polysiloxane diol, at least onepolysiloxane diamine, or a combination thereof and the optional at leastone polyol (e.g., present in the second component of the firstembodiment). Alternatively, according to certain embodiments of thefirst embodiment, the foaming agent does not comprise part of the kitbut is added to the components of the kit at the time of addition of thedegradable foam into the pneumatic tire. Various foaming agents suitablefor use in preparing foams including polyurethane foams are well known.Non-limiting examples of suitable foaming agents for use in thoseembodiments of the first-fourth embodiments that utilize a foaming agentinclude water, hydrocarbons (e.g., propane, butane, pentane),halocarbons (e.g., fluorocarbons, chlorofluorocarbons), air, carbondioxide, azodicarbonamide, and combinations thereof. In literaturerelating to production of foams such as polyurethane foams, foamingagents are often referred to as blowing agents, and, thus, blowingagents known to be useful for producing polyurethane foams can beutilized as the foaming agent in certain embodiments of the first-fourthembodiments disclosed herein. The amount of foaming agent utilized is arelatively minor amount such as no more than 5%, no more than 3%, nomore than 1% by weight of the total amount of di- or polyisocyanate; atleast one polysiloxane diol, at least one polysiloxane diamine, or acombination thereof; and any polyol.

Catalyst(s)

In certain embodiments of the first-fourth embodiments, at least onecatalyst is included in the ingredients of the kit, ingredients of thefoam or ingredients used to prepare the foam. Catalysts for use inpreparing foams such as polyurethane foams are well known. Suitablecatalysts for use in those embodiments of the first-fourth embodimentswhere at least one catalyst is utilized include, but are not limited to,catalysts typically used in polyurethane production. Non-limitingexamples of suitable catalysts for use in those embodiments of thefirst-fourth embodiments where at least one catalyst is utilized includeorganic amines (e.g., tertiary aliphatic amines, cycloaliphatic amines,aromatic amines) and Lewis-acid organic metal compounds (e.g., tincompounds such as tin(II) salts of organic carboxylic acids, metalcomplexes such as acetyl acetonates of iron, titanium, zinc, aluminum,zirconium, manganese, nickel, and cobalt, zinc carboxylates, cesiumcarboxylates, cobalt carboxylates). In those embodiments of thefirst-fourth embodiments where at least one catalyst is utilized varyingamounts can be utilized; in certain such embodiments, the amount of atleast one catalyst is 0.0001% to 10% by weight, including 0.001 to 5% byweight based upon the total amount (by weight) of di- or polyisocyanate.

Degrading of the Degradable Foam

As discussed above, the degradable foams disclosed herein can bedegraded using a solution comprising either: (a) a source of fluorideanion, or (b) an organic acid having a pKa of less than 2, an inorganicacid having a pKa of less than 2, or a combination thereof andoptionally a solvent for the acid. The components of (a) and (b) can begenerically described as “degradants.” The method of the fourthembodiment includes a step of contacting the degradable foam with asolution comprising one of these degradants; the relative amounts ofdegradant to foam are as discussed above. In certain embodimentsapplicable to the first-fourth embodiments disclosed herein, degradingof the foam can be achieved more quickly or more completely by the useof heat. In certain embodiments where the degradant comprises aninorganic acid, the method of the fourth embodiment preferably includesheating. When heating is utilized, it may comprise heating at atemperature above about 40° C., preferably above about 100° C. Incertain embodiments applicable to the first-fourth embodiments disclosedherein where heating is utilized, it comprises heating at about 120 toabout 250° C., including 120 to 250° C., about 140 to about 200° C., and140 to 200° C. Generally, the heating temperatures disclosed hereinshould be understood as the temperature reached by the combined solutionand degradable foam such as could be measured by insertion of athermometer or thermocouple into a portion of the combined solution andfoam. In certain embodiments applicable to the first-fourth embodimentsdisclosed herein, the heating comprises heating for about 0.5 to about10 hours, including 0.5 to 10 hours, about 0.5 hours to about 5 hours,0.5 hours to 5 hours, about 0.5 hours to about 3 hours, 0.5 hours to 3hours, about 0.5 hours to about 2 hours, 0.5 hours to 2 hours, about 0.5hours to about 1 hour, and 0.5 hours to 1 hour, each time periodincluding but not limited to the foregoing heating temperatures. Theheating temperature utilized will be somewhat dependent upon the amountof time available for degradation of the foam; generally, fasterdegradation will occur at higher temperatures. According to certainembodiments applicable to the first-fourth embodiments disclosed herein,the heating (including at the foregoing temperatures and/or for theforegoing time periods) may be achieved using various methods,non-limiting examples of which include placing the tire containingsolution applied to the foam onto a heater, into a heater, under aheater, or applying directed heat to the tire. Non-limiting examples ofsuitable heaters or heat sources include hot-plate type surfaces, ovens,tire molds, radiant heat sources, and microwaves.

EXAMPLES

The following examples illustrate specific and exemplary embodimentsand/or certain features of the embodiments of the present disclosure.The examples are provided solely for the purposes of illustration andshould not be construed as limiting the present disclosure. Numerousvariations over the specific examples are possible without departingfrom the spirit and scope of the presently disclosed embodiments.

Example 1 (control): A sample of polyurethane foam weighing 10 grams wasobtained; the sample had been cut from a used pneumatic tire that hadbeen filled with the polyurethane foam and utilized on a vehicle. Thepolyurethane foam sample was black in color and generallynon-compressible by hand-squeezing. The polyurethane foam had beenprepared from a combination of a first component (toluene diisocyanateand oil) and a second component (comprising polypropylene oxide,ethylene oxide, and oil) in approximately equal amounts.

Example 2: A degradable foam was prepared according to the followingprocedure. A first component comprising toluene diisocyanate and oil wasutilized. A second component comprising polypropylene oxide and ethyleneoxide was provided. Poly(dimethylsiloxane) hydroxyl terminated (Mn=550grams/mole) was obtained from Sigma- Aldrich Corporation. Thepoly(dimethylsiloxane) hydroxyl terminated was mixed with the secondcomponent in an amount sufficient to comprise 25% by weight of themodified second component (i.e., 1 part poly(dimethylsiloxane) to 3parts original second component). 1.1 parts of the first component and 1part of the modified second component were mixed together and allowed tostand wherein foaming began within minutes, thereby forming a degradablefoam.

Example 3: The degradable foam prepared in Example 2 was degradedaccording to the following procedure. A 10 gram sample of the foam wasmixed with 1.0 milliliters of tetrabutylammonium fluoride (a source offluoride anion). The mixture was allowed to stand at room temperatureovernight on an orbital mixer. When the mixture was observed thefollowing morning, the foam had degraded into a pourable liquid.

Example 4 (control): A 10 gram sample of the foam of Example 1 wassubjected to the same procedure described in Example 3 (i.e., mixed with1.0 milliliters of tetrabutylammonium fluoride under the sameconditions). The control foam which lacked any polysiloxane did notdegrade as a result of contact with the fluoride anion source, insteadretaining its solid and non-compressible form rather than degrading intoa pourable liquid.

As shown by the above examples, the incorporation of polysiloxane into apolyurethane foam results in a degradable foam that is capable ofdegradation into a pourable liquid upon contact with a source offluoride anion.

This application discloses several numerical range limitations thatsupport any range within the disclosed numerical ranges, even though aprecise range limitation may not be stated verbatim in thespecification, because the embodiments of the compositions and methodsdisclosed herein could be practiced throughout the disclosed numericalranges. With respect to the use of substantially any plural or singularterms herein, those having skill in the art can translate from theplural to the singular or from the singular to the plural as isappropriate to the context or application. The various singular orplural permutations may be expressly set forth herein for sake ofclarity.

It will be understood by those within the art that, in general, termsused herein, and especially in the appended claims are generallyintended as “open” terms. For example, the term “including” should beinterpreted as “including but not limited to,” the term “having” shouldbe interpreted as “having at least,” the term “includes” should beinterpreted as “includes but is not limited to.” It will be furtherunderstood by those within the art that if a specific number of anintroduced claim recitation is intended, such an intent will beexplicitly recited in the claim, and in the absence of such recitationno such intent is present. For example, as an aid to understanding, thefollowing appended claims may contain usage of the introductory phrases“at least one” and “one or more” to introduce claim recitations.However, the use of such phrases should not be construed to imply thatthe introduction of a claim recitation by the indefinite articles “a” or“an” limits any particular claim containing such introduced claimrecitation to inventions containing only one such recitation, even whenthe same claim includes the introductory phrases “one or more” or “atleast one” and indefinite articles such as “a” or “an” (e.g., “a” or“an” should typically be interpreted to mean “at least one” or “one ormore”); the same holds true for the use of definite articles used tointroduce claim recitations. In addition, even if a specific number ofan introduced claim recitation is explicitly recited, those skilled inthe art will recognize that such recitation should typically beinterpreted to mean at least the recited number (e.g., the barerecitation of “two recitations,” without other modifiers, typicallymeans at least two recitations, or two or more recitations).Furthermore, in those instances where a convention analogous to “atleast one of A, B, and C, etc.” is used, in general such a constructionis intended in the sense one having skill in the art would understandthe convention (e.g.,“a system having at least one of A, B, and C” wouldinclude but not be limited to systems that have A alone, B alone, Calone, A and B together, A and C together, B and C together, and/or A,B, and C together, etc.). It will be further understood by those withinthe art that virtually any disjunctive word or phrase presenting two ormore alternative terms, whether in the description, claims, or drawings,should be understood to contemplate the possibilities of including oneof the terms, either of the terms, or both terms. For example, thephrase “A or B” will be understood to include the possibilities of “A”or “B” or “A and B.”

All references, including but not limited to patents, patentapplications, and non-patent literature are hereby incorporated byreference herein in their entirety.

While various aspects and embodiments of the compositions and methodshave been disclosed herein, other aspects and embodiments will beapparent to those skilled in the art. The various aspects andembodiments disclosed herein are for purposes of illustration and arenot intended to be limiting, with the true scope and spirit beingindicated by the claims.

What is claimed is:
 1. A method for degrading polyurethane foam frominside of a mounted polyurethane foam-containing tire, the methodcomprising: a. providing a solution comprising at least one phosphorousoxoacid or an ester thereof, b. providing a mounted tire comprising awheel and a rubber carcass and having polyurethane foam inside therubber carcass, c. applying the solution to the polyurethane foam insidethe carcass, and d. heating to degrade the polyurethane foam.
 2. Themethod of claim 1, wherein the at least one phosphorous oxoacid or anester thereof comprises an ester which is optionally halogenated.
 3. Themethod of claim 2, wherein the ester comprises at least one of: a. adiester; b. a monoester; or c. a triester.
 4. The method of claim 2wherein the ester functionality comprises an alkyl group eachindependently selected from C1-C41 optionally substituted with one ormore halogen, or an aromatic or heteroaromatic group selected fromC5-C53 optionally substituted with one or more halogen.
 5. The method ofclaim 1, wherein the at least one phosphorous oxoacid or ester thereofcomprises dimethyl phosphonate, diethyl phosphonate, or a combinationthereof.
 6. The method of claim 1, wherein the solution is applied tothe foam in a volume/volume ratio of about 10/1 to about 1/1, or theamount of degradant in the polyurethane foam is about 50 to about 300%by weight of the polyurethane foam.
 7. The method of claim 1, whereinthe heating comprises at least one of: a. heating at about 120 to about250° C., preferably about 140 to about 200° C.; or b. heating for about0.5 to about 10 hours, preferably about 0.5 hours to about 5 hours. 8.The method of claim 1, further comprising exposing at least a portion ofthe foam prior to applying the solution.
 9. The method of claim 1,wherein the mounted tire further comprises a tire stem and applying ofthe solution comprises adding the solution through the tire stem. 10.The method of claim 1, wherein the solution comprising at least onephosphorous oxoacid or an ester thereof further comprises at least onecatalyst, at least one surfactant, a combination thereof.
 11. A methodfor separating a wheel from a mounted polyurethane foam anddegradant-containing tire by degrading the foam, the method comprising:a. providing a mounted tire comprising a wheel and a rubber carcass withpolyurethane foam inside the rubber carcass wherein the polyurethanefoam includes a degradant comprising at least one phosphorous oxoacid oran ester thereof, b. optionally applying a solution comprising at leastone phosphorous oxoacid or an ester thereof to the polyurethane foaminside the rubber carcass, c. heating to degrade the polyurethane foam,and d. separating the wheel from the rubber carcass.
 12. The method ofclaim 11, wherein the at least one phosphorous oxoacid or an esterthereof comprises an ester which is optionally halogenated.
 13. Themethod of claim 12, wherein the ester comprises at least one of: a. adiester; b. a monoester; or c. a triester.